Organoleptic compounds

ABSTRACT

The present invention is directed to novel fragrance compounds and their unexpected advantageous use in enhancing, improving or modifying a fragrance formulation through the addition of an olfactory acceptable amount of the compounds, wherein the compounds are represented by the following formula: 
     
       
         
         
             
             
         
       
         
         
           
             wherein the dotted line represents a single or double bond, and 
             R is selected from the group consisting of propyl, butyl, and pentyl.

STATUS OF RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 12/908,038,filed Oct. 20, 2010 now U.S. Pat. No. 8,080,691, which is acontinuation-in-part of U.S. Ser. No. 12/692,682, filed Jan. 25, 2010,now U.S. Pat. No. 7,842,659, which is a continuation-in-part of U.S.Ser. No. 11/958,038, filed Dec. 17, 2007, now U.S. Pat. No. 7,678,749,the contents hereby incorporated by references as if set forth in theirentirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how small differences in chemical structurescan result in unexpected and significant differences in odor, notes andcharacteristics of molecules. These variations allow perfumers and otherpersons to apply new compounds in creating new fragrances.

The synthesis of natural bicycle[3.2.1]octane products has beenpreviously reported. The interest is driven by the biological activitiesthat some of these natural products display. The major function has beenshown in plant growth and development, and these products may alsoprovide some medicinal benefits. However, the chemistry of naturalbicycle[3.2.1]octane products is rich and diverse, no further propertiesof any of these natural products were reported [Mander, Chem. Rev. 92:573-612 (1992); Nakajima et al., Tetr. Lett. 35(51): 9597-9600 (1994);Beyersbergen van Henegouwen et al., J. Org. Chem. 62(25): 8862-8867(1997); Dai et al., Adv. Synth. Catal. 348(16-17): 2449-2456 (2006)].

SUMMARY OF THE INVENTION

The present invention provides novel chemicals and their unexpectedadvantageous use in enhancing, improving or modifying the fragrance ofperfumes, colognes, toilet waters, personal products, fabric careproducts, and the like.

One embodiment of the present invention is directed to a novel fragrancecompound represented by the following formula:

-   -   wherein the dotted line represents a single or double bond;    -   R is selected from the group consisting of propyl, butyl, and        pentyl; and    -   R¹ and R² together represent ═O or a ring structure represented        by

Another embodiment of the present invention is directed to a novelfragrance compound that exhibits unexpected strong fragrance effect,whereby the fragrance compound is represented by the following formula:

-   -   wherein the dotted line and R are as defined above.

Another embodiment of the present invention is directed to the use ofthe compounds provided above as fragrance materials in perfumes,colognes, toilet waters, personal products, fabric care products, andthe like.

Another embodiment of the present invention is directed to a fragrancecomposition comprising the compounds provided above.

Another embodiment of the present invention is directed to a fragranceproduct comprising the compounds provided above.

Another embodiment of the present invention is directed to a method ofimproving, enhancing or modifying a fragrance formulation byincorporating an olfactory acceptable amount of the compounds providedabove.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

It has been surprisingly found that the compounds of the presentinvention provide unexpected strong green and herbal characteristics.

In one embodiment of the present invention, the compounds of the presentinvention are represented by the following structures:

Those with skill in the art will recognize that:

Structure III is 3-propylbicyclo[3.2.1]oct-6-en-2-one;

Structure IV is 3-propylbicyclo[3.2.1]octan-2-one;

Structure V is 3-butylbicyclo[3.2.1]oct-6-en-2-one;

Structure VI is 3-butylbicyclo[3.2.1]octan-2-one;

Structure VII is 3-pentylbicyclo[3.2.1]oct-6-en-2-one; and

Structure VIII is 3-pentylbicyclo[3.2.1]octan-2-one.

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as high performance liquid chromatography,referred to as HPLC, and particularly gel chromatography and solid phasemicroextraction, referred to as SPME.

The compounds of the present invention were prepared with correspondingaldehydes according to the following reaction schemes, the details ofwhich are specified in the Examples. The starting materials andcatalysts were purchased from Aldrich Chemical Company.

-   -   wherein R is as defined above; and    -   Pd/C represents palladium carbon catalyst.

The compounds of the present invention, for example, possess thefollowing fragrance notes:

3-Propylbicyclo[3.2.1]oct-6-en-2-one (Structure III) possesses stronggreen, herbaceous, fresh, clean, natural, floral, and woody notes;

3-butylbicyclo[3.2.1]oct-6-en-2-one (Structure V) possesses strongfruity, green, herbal, and celery notes;

3-butylbicyclo[3.2.1]octan-2-one (Structure VI) possesses strongcoconut, lactonic, woody, minty, jasmine cis like, anisic, and tuberosenotes;

3-pentylbicyclo[3.2.1]oct-6-en-2-one (Structure VII) possesses stronganisic, fruity, spicy, mossy, herbal, and celery notes; and

3-pentylbicyclo[3.2.1]octan-2-one (Structure VIII) possesses strongsweet, slight anisic, floral, and celery notes.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products, fabric care products as well as airfresheners and cosmetic preparations. These compounds can also be usedto perfume cleaning agents, such as, but not limited to detergents,dishwashing materials, scrubbing compositions, window cleaners and thelike. In these preparations, the compounds of the present invention canbe used alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk; and flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

The compounds of the present invention can be used in combination with acomplementary fragrance compound. The term “complementary fragrancecompound” as used herein is defined as a fragrance compound selectedfrom the group consisting of 2-[(4-methylphenyl)methylene]-heptanal(Acalea), iso-amyl oxyacetic acid allylester (Allyl Amyl Glycolate),(3,3-dimethylcyclohexyl)ethyl ethyl propane-1,3-dioate (Applelide),2-ethyl-4-(2,2,3-trimethyl-3-cyclo-penten-1-yl)-2-buten-1-ol (Bacdanol),2-methyl-3-[(1,7,7-trimethylbicyclo[2.2.1]hept-2-yl)oxy]exo-1-propanol(Bornafix), 1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one(Cashmeran), 1,1-dimethoxy-3,7-dimethyl-2,6-octadiene (Citral DMA),3,7-dimethyl-6-octen-1-ol (Citronellol),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl acetate (Cyclacet),3A,4,5,6,7,7A-hexahydro-4,7-methano-1H-inden-5/6-yl propinoate(Cyclaprop), 3A,4,5,6,7,7A-hexahydro-4,7-methano-1G-inden-5/6-ylbutyrate (Cyclobutanate),1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one (Delta Damascone),3-(4-ethylphenyl)-2,2-dimethyl propanenitrile (Fleuranil),3-(O/P-ethylphenyl) 2,2-dimethyl propionaldehyde (Floralozone),tetrahydro-4-methyl-2-(2-methylpropyl)-2H-pyran-4-ol (Floriffol),1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran(Galaxolide), 1-(5,5-dimethyl-1-cyclohexen-1-yl)pent-4-en-1-one(Galbascone), E/Z-3,7-dimethyl-2,6-octadien-1-yl acetate (GeranylAcetate), α-methyl-1,3-benzodioxole-5-propanal (Helional),1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one (Hexylon),(Z)-3-hexenyl-2-hydroxybenzoate (Hexenyl Salicylate, CIS-3),4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (Ionone α),1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one(Iso E Super), methyl 3-oxo-2-pentylcyclopentaneacetate (Kharismal),2,2,4-trimethyl-4-phenyl-butanenitrile (Khusinil),3,4,5,6,6-pentamethylhept-3-en-2-one (Koavone),3/4-(4-hydroxy-4-methyl-pentyl)cyclohexene-1-carboxaldehyde (Lyral),3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one (MethylIonone γ), 1-(2,6,6-trimethyl-2-cyclohexen-1-yl) pent-1-en-3-one (MethylIonone α Extra, Methyl Ionone N), 3-methyl-4-phenylbutan-2-ol(Muguesia), cyclopentadec-4-en-1-one (Musk Z4),3,3,4,5,5-pentamethyl-11,13-dioxatricyclo[7.4.0.0<2,6>]tridec-2(6)-ene(Nebulone), 3,7-dimethyl-2,6-octadien-1-yl acetate (Neryl Acetate),3,7-dimethyl-1,3,6-octatriene (Ocimene), ortho-tolylethanol (Peomosa),3-methyl-5-phenylpentanol (Phenoxanol),1-methyl-4-(4-methyl-3-pentenyl)cyclohex-3-ene-1-carboxaldehyde(Precyclemone B),2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sanjinol),2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol(Santaliff), Terpineol, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde(Triplal), decahydro-2,6,6,7,8,8-hexamethyl-2H-indeno[4,5-B]furan(Trisamber), 2-tert-butylcyclohexyl acetate (Verdox),4-tert-butylcyclohexyL acetate (Vertenex), acetyl cedrene (Vertofix),3,6/4,6-dimethylcyclohex-3-ene-1-carboxaldehyde (Vertoliff), and(3Z)-1-[(2-methyl-2-propenyl)oxy]-3-hexene (Vivaldie).

The terms “fragrance formulation”, “fragrance composition”, and “perfumecomposition” mean the same and refer to a consumer composition that is amixture of compounds including, for example, alcohols, aldehydes,ketones, esters, ethers, lactones, nitriles, natural oils, syntheticoils, and mercaptans, which are admixed so that the combined odors ofthe individual components produce a pleasant or desired fragrance. Thefragrance formulation of the present invention is a consumer compositioncomprising a compound of the present invention and further acomplementary fragrance compound as defined above.

The term “fragrance product” means a consumer product that adds afragrance or masks a malodor. Fragrance products may include, forexample, perfumes, colognes, personal care products such as soaps,shower gels, and hair care products, fabric products, air fresheners,cosmetic preparations, and perfume cleaning agents such as detergents,dishwashing materials, scrubbing compositions, and window cleaners. Thefragrance product of the present invention is a consumer product thatcontains a compound of the present invention and further a complementaryfragrance compound as defined above.

The term “improving” in the phrase “improving, enhancing or modifying afragrance formulation” is understood to mean raising the fragranceformulation to a more desirable character. The term “enhancing” isunderstood to mean making the fragrance formulation greater ineffectiveness or providing the fragrance formulation with an improvedcharacter. The term “modifying” is understood to mean providing thefragrance formulation with a change in character.

Olfactory acceptable amount is understood to mean the amount of acompound in a perfume composition. The compound will contribute itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of a perfume composition,or by modifying the olfactory reaction contributed by another ingredientin the composition. The amount will vary depending on many factorsincluding other ingredients, their relative amounts and the effect thatis desired.

The amount of the compounds of the present invention employed in afragrance formulation varies from about 0.005 to about 70 weightpercent, preferably from 0.005 to about 10 weight percent, morepreferably from about 0.5 to about 8 weight percent, and even morepreferably from about 1 to about 7 weight percent. Those with skill inthe art will be able to employ the desired amount to provide desiredfragrance effect and intensity. In addition to the compounds of thepresent invention, other materials can also be used in conjunction withthe fragrance formulation. Well known materials such as surfactants,emulsifiers, polymers to encapsulate the fragrance can also be employedwithout departing from the scope of the present invention.

When used in a fragrance formulation this ingredient provides green andherbal notes that make the fragrance formulation more desirable andnoticeable and add the perception of value. All of the odor qualitiesfound in this material assist in beautifying and enhancing the finishedaccord improving the performance of the other materials in thefragrance. There is also the fruity side of it which is found in manyfragrances today which happens to be very trendy, especially for theyounger consumers.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. The chemical materials used inthe preparation of the compounds of the present invention arecommercially available from Aldrich Chemical Company. As used herein allpercentages are weight percent unless otherwise noted, ppm is understoodto stand for parts per million, L is understood to be liter, mL isunderstood to be milliliter, Kg is understood to be kilogram, and g begram. IFF as used in the examples is understood to mean InternationalFlavors & Fragrances Inc., New York, N.Y., USA.

Example I

Preparation of 2-Propylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde: A 5-Lflask fitted with an overhead stirrer and a condenser was charged withdi-n-butylamine (75 g) and acetic acid (70 g). Formaldehyde solution inwater (1.3 L, 37%) was added and the resulting solution was heated to50° C. with stirring. Pentanal (1 Kg) was then fed in over about 2hours. After the feed was completed the temperature was maintained at50° C. for 1 hour and then cooled to room temperature. The reactionmixture was poured into a separatory funnel. The organic layer waswashed with water and purified by distillation to yield 2-methylenepentanal (820 g).2-Methylene pentanal (302 g) and dicyclopentadiene (244 g) were loadedinto a 2-L autoclave. The autoclave was sealed and heated to 170° C. Thereaction was monitored by Gas Chromatography (“GC”) analysis, whichshowed the completion after 3 hours. The reaction was cooled to roomtemperature. The crude product was purified by distillation to yield2-propylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde (136 g).Product 2-methylene pentanal had the following NMR spectralcharacteristics:

¹H NMR (CDCl₃, 500 MHz): 0.90 ppm (t, 3H, J=7 Hz), 1.48 ppm (q, 2H,J=7.5 Hz), 2.22 ppm (t, J=7.5 Hz), 5.99 ppm (s, 1H), 6.24 ppm (s, 1H),9.54 ppm (s, 1H).

Product 2-propylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde had thefollowing NMR spectral characteristics:

¹H NMR (CDCl₃, 500 MHz): 0.84 ppm (t, 3H, J=7.2 Hz), 1.11-1.39 ppm (m,6H), 1.49-1.57 ppm (m, 1H), 2.16 ppm (m, 1H), 2.85 ppm (s, 1H), 2.93 ppm(s, 1H), 6.07 ppm (dd, 1H, J=5.37, 3.13 Hz), 6.27 ppm (dd, 1H, J=5.33,3.08 Hz), 9.70 ppm (s, 1H).

Example II

Preparation of 3-Propylbicyclo[3.2.1]oct-6-en-2-one (Structure III):Aluminum chloride (AlCl₃, 110 g) was suspended in toluene (1 L) andchilled to −30° C. using a dry ice/isopropanol bath.2-Propylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde (136 g, synthesized asabove) was fed in using an addition funnel over 1 hour while thetemperature was maintained at −30° C. After the feed was completed thetemperature was allowed to rise to 0° C. GC analysis showed the reactionwas completed after 40 minutes. The reaction mixture was then pouredonto H₂SO₄ (1 L, 20%) over ice. The resulting biphasic mixture wasshaken to split the organic and aqueous layers. The aqueous layer waswashed once with toluene (300 mL) and combined with the organic layers.The mixture was then washed with NaOH solution (750 mL, 10%), followedby water until the water was tested neutral. The resulting organicmaterial was purified by distillation to yield3-propylbicyclo[3.2.1]oct-6-en-2-one (92 g).

¹H NMR (CDCl₃, 500 MHz): 0.87 ppm (t, 3H, J=7.2 Hz), 1.16-1.37 ppm (m,3H), 1.44-1.50 ppm (m, 1H), 1.72-1.81 ppm (m, 1H), 1.83-2.00 ppm (m,⅔H), 2.12-2.4 ppm (m, 2H), 2.38-2.52 ppm (m, 1H), 2.64-2.70 ppm (m, ⅓H),2.77-2.86 (m, 1H), 3.00-3.06 ppm (m, 1H), 5.80 ppm (dd, ⅔H, J=5.4, 3.1Hz), 6.05 ppm (dd, ⅓H, J=5.7, 2.9 Hz), 6.21-6.26 ppm (m, 1H).

3-Propylbicyclo[3.2.1]oct-6-en-2-one, possessed strong green,herbaceous, fresh, clean, natural, floral, and woody notes.

Example III

Preparation of 2-Butylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde: A 5-Lflask fitted with an overhead stirrer and a condenser was charged withdi-n-butylamine (77 g) and acetic acid (72 g). Formaldehyde solution inwater (1.1 L, 37%) was added and the resulting solution was heated to50° C. with stirring. Hexanal (1 Kg) was then fed in over about 2 hours.After GC analysis showed the completion of the reaction, the reactionmixture was cooled to room temperature, poured into a separatory funnel,and washed once with HCl solution (5%). The organic layer was thenwashed with saturated sodium bicarbonate to provide crude 2-methylenehexanal (727 g), which was loaded into a 2-L stainless steel pressurereactor along with dicyclopentadiene (511 g). The pressure reactor wassealed and heated to 170° C. with stirring for two hours. The reactionwas then cooled to room temperature. The resulting crude product waspurified by distillation to yield2-butylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde (570 g).

Example IV

Preparation of 3-Butylbicyclo[3.2.1]oct-6-en-2-one (Structure V):2-Butylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde (570 g, synthesized asabove) was loaded into a 3-L round bottom flask fitted with an overheadstirrer and a condenser, followed by methylene chloride (CH₂Cl₂, 1 L).The resulting solution was cooled to −50° C. using a dry ice bath.Anhydrous aluminum chloride (AlCl₃, 215 g) was then added in oneportion. The light yellow solution changed color to orange, then darkred with a simultaneous increase in reaction temperature, up to about−30° C. The reaction temperature was allowed to gradually increase to15° C. GC analysis showed the completion of the reaction after 1 hour.The reaction mixture was then poured onto ice and sulfuric acid (10%),and the organic layers were separated and washed once with sodiumhydroxide solution (10%). The solvent (CH₂Cl₂) was removed under reducedpressure, and the resulting crude product was purified by distillationto yield 2-butylbicyclo[2.2.1]oct-6-en-2-one (224 g).

¹H NMR (CDCl₃, 500 MHz): 0.88 ppm (t, 3H, J=7.03 Hz), 1.18-1.38 ppm (m,5H+˜20% of 1H), 1.44-1.50 ppm (m, ˜80% of 1H), 1.75-1.85 (m, ˜80% of1H), 1.84 ppm (d, 1H, J=11.1 Hz), 1.94-1.99 ppm (m, ˜80% of 1H),2.12-2.25 ppm (m, ˜20% of 3H), 2.39-2.52 (m, 1H), 2.64-2.71 (m, ˜80% of1H), 2.77-2.88 ppm (m, 1H), 3.00-3.07 ppm (m, 1H), 5.78-5.82 ppm (m,˜20% of 1H), 6.02-6.07 ppm (dd, ˜80% of 1H, J=5.29, 2.82 Hz), 6.19-6.28ppm (dd, 1H, J=5.55, 2.65 Hz).

3-Butylbicyclo[3.2.1]oct-6-en-2-one possessed strong fruity, green,herbal, and celery notes.

Example V

Preparation of 3-Butylbicyclo[3.2.1]octan-2-one (Structure VI):3-Butylbicyclo[3.2.1]oct-6-en-2-one (100 g, synthesized as above) wasplaced in a stainless steel autoclave with isopropanol (50 g) andpalladium on carbon (Pd/C, 1 g). The mixture was placed under 300 psi ofhydrogen gas (H₂) and heated at 100° C. until gas uptake ceased. Theresulting material was removed from the autoclave, filtered, anddistilled to yield 3-butylbicyclo[3.2.1]octan-2-one (55 g).

¹H NMR (CDCl₃, 500 MHz): 0.99 ppm (t, 3H, J=7.11 Hz), 1.11-1.34 ppm (m,6H), 1.65-1.75 ppm (m, 3H), 1.76-1.88 ppm (m, 3H), 1.90-2.02 ppm (m,2H), 2.24-2.34 ppm (m, 1H), 2.39-2.44 ppm (m, 1H), 2.70-2.74 ppm (m,1H).

3-Butylbicyclo[3.2.1]octan-2-one possessed strong coconut, lactonic,woody, minty, jasmine cis like, anisic, and tuberose notes.

Example VI

Preparation of 2-Pentylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde: A 3-Lthree-neck flask fitted with an overhead stirrer and a condenser wascharged with di-n-butylamine (33 g) and acetic acid (31 g). Formaldehydesolution in water (500 mL, 33%) was added and the resulting solution washeated to 50° C. with stirring. Heptanal (500 g) was fed in over about1.5 hours. A slight exotherm was noticed during the feed. GC analysisshowed the consumption of heptanal and the production of 2-methyleneheptanal, and a conversion rate of about 95% after the feed wascompleted. The reaction was cooled to room temperature and the reactionmixture was poured into a separatory funnel and washed once with HClsolution (5%). The organic layer was then washed once with saturatedsodium carbonate to provide crude 2-methylene heptanal (553 g), whichwas loaded into a 2-L stainless steel pressure reactor along withdicyclopentadiene (343 g). The pressure reactor was sealed and heated to170° C. with stirring for two hours. The reaction was then cooled toroom temperature. The resulting crude product was purified bydistillation to yield 2-pentylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde(217 g).

Example VII

Preparation of 3-Pentylbicyclo[3.2.1]oct-6-en-2-one (Structure VII):2-Pentylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde (217 g, synthesized asabove) was loaded into a 2-L round bottom flask fitted with an overheardstirrer and a condenser, followed by CH₂Cl₂ (1 L). The resulting mixturewas cooled to 0° C. using a dry ice bath. AlCl₃ (153 g) was then addedin one portion. After GC analysis showed the completion of the reaction,the reaction mixture was poured onto ice, and the organic layers wereseparated and washed once with sodium hydroxide solution (10%). Thesolvent (CH₂Cl₂) was then removed under reduced pressure, and theresulting crude product was purified by distillation to yield3-pentylbicyclo[3.2.1]oct-6-en-2-one (100 g).

¹H NMR (CDCl₃, 500 MHz): 0.87 ppm (t, 3H, J=7.05 Hz), 1.16-1.36 ppm (m,8H), 1.76-1.83 ppm (m, 1H), 2.11-2.24 ppm (m, 3H), 2.44-2.50 ppm (m,1H), 2.78 (s, 1H), 3.05 ppm (t, 1H, J=3.69 Hz), 5.80 ppm (dd, 1H,J=5.12, 3.31 Hz), 6.24 (dd, 1H, J=5.29, 2.91 Hz).

3-Pentylbicyclo[3.2.1]oct-6-en-2-one possessed strong anisic, fruity,spicy, mossy, herbal, and celery notes.

Example VIII

Preparation of 3-Pentylbicyclo[3.2.1]octan-2-one (Structure VIII):3-Pentylbicyclo[3.2.1]oct-6-en-2-one (130 g, synthesized as above) wasplaced in a stainless steel autoclave with isopropanol (30 g) and Pd/C(1.5 g). The mixture was placed under 300 psi of hydrogen gas, andheated at 100° C. until gas uptake ceased. The resulting material wasthen removed from the autoclave, filtered, and distilled to yield3-pentylbicyclo[3.2.1]octan-2-one 70 g).

¹H NMR (CDCl₃, 500 MHz): 0.88 ppm (t, 3H, J=6.89 Hz), 1.10-1.18 ppm (m,1H), 1.19-1.37 ppm (m, 7H), 1.65-1.89 ppm (m, 6H), 1.90-2.03 ppm (m,2H), 2.25-2.34 ppm (m, 1H), 2.41-2.45 ppm (m, 1H), 2.73 ppm (t, 1H,J=5.62 Hz).

3-Pentylbicyclo[3.2.1]octan-2-one possessed strong sweet, slight anisic,floral, and celery notes.

Example IX

The fragrance properties of the above compounds (i.e., StructuresII-VII) were evaluated using an intensity scale of 0 to 3, where 0=none,1=weak, 2=moderate, 3=strong. Averaged sensory scores were reported inthe following:

Odor No. Compound Chemical Name Odor Profile Intensity 1

3-propylbicyclo[3.2.1]oct-6- en-2-one (Structure III) Green, herbaceous,fresh, clean, natural, floral, and woody 3 2

3-butylbicyclo[3.2.1]oct-6- en-2-one (Structure V) Fruity, green,herbal, and celery 3 3

3-butylbicyclo[3.2.1]octan- 2-one (Structure VI) Coconut, lactonic,woody, minty, jasmine cis like, anisic, and tuberose 3 4

3-pentylbicyclo[3.2.1]oct-6- en-2-one (Structure VII) Anisic, fruity,spicy, mossy, herbal, and celery 3 5

3-pentylbicyclo[3.2.1]octan- 2-one (Structure VIII) Sweet, slightanisic, floral, and celery 3 6

3-hexylbicyclo[3.2.1]oct-6- en-2-one Fruity, floral, sweet, andaldehydic 1 7

3-heptylbicyclo[3.2.1]oct-6- en-2-one Weak, methyl sal like, slightfruity 1

Example IX (Continued)

Compound No.s. 1-5 (i.e., Structures III, V, VI, VII, and VIII)exhibited unexpected strong and long-lasting odor, superior to CompoundNo. 6, which contains a hexyl group, and Compound No. 7, which containsa heptyl group.

Example X Fragrance Formulation Containing3-propylbicyclo[3.2.1]oct-6-en-2-one (Structure III):

Fragrance Ingredient Parts by Wt Allyl Amyl Glycolate BHT 2.00 AmberiffCryst 0.30 Bergamot oil Italy MPF “PFG” BLO BHT 10.00 Citral DMA 0.50Citroflex #2 Pfizer 4.30 Damascone Delta BHT 0.10 Dihydro Myrcenol 14.70Dipropylene Glycol 5.00 3-Propylbicyclo[3.2.1]oct-6-en-2-one 5.00(Structure III) Geranium Bourbon Type 0.20 Helional 0.30 Iso E Super BHT5.00 Kharismal 3.00 Lavandin 4066C WO Color LMR 0.40 Linalyl Acet Super3.00 Lyral BHT 4.00 Meth Beta Naph Ketone 0.50 Meth Ionone N BHT 20.00Muguesia 0.20 Nebulone (ELINCS) 12.00 Peomosa 1.00 Polysantol (ELINCS)MVB 1.00 Precyclemone B BHT 1.00 Undecavertol MVB 1.00 Vertofix Coeur5.00 Total: 100.003-Propylbicyclo[3.2.1]oct-6-en-2-one imparts green, herbaceous, fresh,clean, natural, floral, and woody characters to a fragrance formula.

Example XI Fragrance Formulation Containing3-butylbicyclo[3.2.1]oct-6-en-2-one (Structure V):

Fragrance Ingredient Parts by Wt Acetald DEA 0.28 Ald C-10 BHA 0.70Allyl Amyl Glycolate BHT 0.1% DPG 1.40 Benz Acet 0.70 Calone 1% DPG 1.40Coumarin 0.28 Dihydro Myrcenol 6.99 Dimeth Benz Carb Acet 6.993-Butylbicyclo[3.2.1]oct-6-en-2-one 5.00 (Structure V) Eth-2-Meth Buty5.59 Eth Vanillin 0.14 Fleuranil (ELINCS) 10% DPG 1.40 Galaxolide 50 PCTDPG 6.99 Galbascone BHT 10% DPG 0.14 Cyclobutanate (ELINCS) 0.28 HexylButy 1.40 Hexyl Cinn Ald BHA/BHT 6.99 Ionol CP 0.14 Iso E Super BHT 6.99Koavone 1.40 Mandarin Oil HP “PFG” 2.80 Mango Ester 0.01 PCT DPG 1% DPG1.40 Meth Anth (USDEA) 0.70 Orange Oil CP “PFG” 2.80 Undecalactone GammaCoeur 1.40 Phenyl Acet 4.20 Vertoliff 6.99 Trisamber (ELINCS) 1% DPG0.70 Nebulone (ELINCS) 6.99 Undecavertol MVB 2.69 Vivaldie (ELINCS) 0.14Verdox 13.99 Total: 100.003-Butylbicyclo[3.2.1]oct-6-en-2-one imparts fruity, green, herbal, andcelery characters to a fragrance formula.

Example XII Fragrance Formulation Containing3-pentylbicyclo[3.2.1]oct-6-en-2-one (Structure VII):

Fragrance Ingredient Parts by Wt Acalea BHT/BHA 3.70 Ald C-8 BHT 0.14Applelide (ELINCS) Stabiliff 6.89 Benz Acet 3.45 Benz Alc 6.89 Benz Prop3.45 Citronellol Coeur 6.89 Cyclaprop 1.03 Cyclemax 0.69 Dimeth BenzCarb Buty 8.27 3-Pentylbicyclo[3.2.1]oct-6-en-2-one 5.00 (Structure VII)Eth Caproate 0.69 Eth Vanillin 0.07 Eth-2-Meth Buty 0.14 Floralozone1.38 Geranyl Acet Pure 2.07 Helional 0.14 Hexalon BHT 0.69 Hexenyl Sal,Cis-3 0.28 Hexyl Cinn Ald BHA/BHT 4.13 Hexyl Sal 0.07 Iso Cyclemone EBHT 0.41 Kharismal 4.35 Lilial 6.89 Linalool Syn 5.51 Linalyl Acet 1.38Meth Cinnamate 0.69 Meth Ionone Alpha Extra BHT 0.34 Muguesia 2.07 NerolCoeur 3.45 Neryl Acet A 0.14 Ocimene BHT 0.07 Orange Oil Nova Decol LMR2.76 Phen Eth Alc White Extra 1.72 Styralyl Acet 0.07 Terpineol Coeur1.38 Undecalactone Gamma Coeur 0.69 Verdox 5.17 Vertenex 6.85 Total:100.003-Pentylbicyclo[3.2.1]oct-6-en-2-one imparts anisic, fruity, spicy,mossy, herbal, and celery characters to a fragrance formula.

What is claimed is:
 1. A fragrance formulation comprising (i) anolfactory effective amount of a compound:

wherein the dotted line represents a single or double bond, and R isselected from the group consisting of propyl, butyl, and pentyl; and(ii) a complementary fragrance compound.
 2. The fragrance formulation ofclaim 1, wherein the compound is 3-propylbicyclo[3.2.1]oct-6-en-2-one.3. The fragrance formulation of claim 1, wherein the compound is3-butylbicyclo[3.2.1]oct-6-en-2-one.
 4. The fragrance formulation ofclaim 1, wherein the compound is 3-butylbicyclo[3.2.1]octan-2-one. 5.The fragrance formulation of claim 1, wherein the compound is3-pentylbicyclo[3.2.1]oct-6-en-2-one.
 6. The fragrance formulation ofclaim 1, wherein the compound is 3-pentylbicyclo[3.2.1]octan-2-one. 7.The fragrance formulation of claim 1 incorporated into a productselected from the group consisting of a perfume, a cologne, toiletwater, a cosmetic product, a personal care product, a fabric careproduct, a cleaning product, and an air freshener.
 8. The fragranceformulation of claim 7, wherein the cleaning product is selected fromthe group consisting of a detergent, a dishwashing composition, ascrubbing compound, and a window cleaner.
 9. The fragrance formulationof claim 1, wherein the olfactory effective amount is from about 0.005to about 10 weight percent.
 10. The fragrance formulation of claim 1,wherein the olfactory effective amount is from about 0.5 to about 8weight percent.
 11. The fragrance formulation of claim 1, wherein theolfactory effective amount is from about 1 to about 7 weight percent.12. A fragrance product comprising (i) an olfactory effective amount ofa compound:

wherein the dotted line represents a single or double bond, and R isselected from the group consisting of propyl, butyl, and pentyl; and(ii) a complementary fragrance compound.
 13. The fragrance product ofclaim 12, wherein the compound is 3-propylbicyclo[3.2.1]oct-6-en-2-one.14. The fragrance product of claim 12, wherein the compound is3-butylbicyclo[3.2.1]oct-6-en-2-one.
 15. The fragrance product of claim12, wherein the compound is 3-butylbicyclo[3.2.1]octan-2-one.
 16. Thefragrance product of claim 12, wherein the compound is3-pentylbicyclo[3.2.1]oct-6-en-2-one.
 17. The fragrance product of claim12, wherein the compound is 3-pentylbicyclo[3.2.1]octan-2-one.